CN103733290B - Method for assembling hybrid electrochemical system - Google Patents
Method for assembling hybrid electrochemical system Download PDFInfo
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- CN103733290B CN103733290B CN201280028163.XA CN201280028163A CN103733290B CN 103733290 B CN103733290 B CN 103733290B CN 201280028163 A CN201280028163 A CN 201280028163A CN 103733290 B CN103733290 B CN 103733290B
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- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000007600 charging Methods 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 27
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 22
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000003990 capacitor Substances 0.000 claims abstract description 20
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims abstract description 15
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 150000002596 lactones Chemical class 0.000 claims abstract description 3
- 239000003575 carbonaceous material Substances 0.000 claims abstract 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 48
- 229910052799 carbon Inorganic materials 0.000 claims description 34
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims description 20
- 239000006229 carbon black Substances 0.000 claims description 17
- 230000008859 change Effects 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 230000005611 electricity Effects 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 7
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 6
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002466 imines Chemical class 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910021401 carbide-derived carbon Inorganic materials 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 241000234282 Allium Species 0.000 claims description 3
- 235000002732 Allium cepa var. cepa Nutrition 0.000 claims description 3
- 125000002015 acyclic group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 241001232809 Chorista Species 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- RCIJMMSZBQEWKW-UHFFFAOYSA-N methyl propan-2-yl carbonate Chemical compound COC(=O)OC(C)C RCIJMMSZBQEWKW-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 210000000262 cochlear duct Anatomy 0.000 claims 1
- 239000006258 conductive agent Substances 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 26
- 150000002500 ions Chemical class 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 4
- 230000004087 circulation Effects 0.000 description 40
- 239000003792 electrolyte Substances 0.000 description 34
- 238000003780 insertion Methods 0.000 description 22
- 230000037431 insertion Effects 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 208000028659 discharge Diseases 0.000 description 14
- 239000002033 PVDF binder Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 11
- 239000007772 electrode material Substances 0.000 description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 9
- 238000002161 passivation Methods 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 238000001994 activation Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 6
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 5
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- 229920001519 homopolymer Polymers 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000006184 cosolvent Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000004769 chrono-potentiometry Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- -1 ion compound Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003180 beta-lactone group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000000457 gamma-lactone group Chemical group 0.000 description 1
- RRMGGYGDQCMPKP-UHFFFAOYSA-N gold lithium Chemical compound [Li].[Au] RRMGGYGDQCMPKP-UHFFFAOYSA-N 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
Method the present invention relates to be used to develop hybrid super capacitor, methods described includes：In at least one stage being assemblied together by the negative electrode being made up of at least one non-porous carbon material and by the enough positive electrodes of at least one porous carbon materials, the electrode is disconnected from each other by least one separator impregnated with the liquid electrolyte of at least one lithium salts for including being dissolved at least one solvent；And, subsequent at least one first charging stages, wherein methods described is characterised by：a）Lithium concentration in liquid electrolyte before the first charging stage is more than or equal to 1.6mol/L；b）At least 50wt% of the lithium salts of liquid electrolyte includes the salt selected from LiTFSI and its derivative；c）At least 80vol% of the solvent of liquid electrolyte is comprising selected from preparing cyclic alkyl carbonate, acyclic alkyl carbonic ester, lactone, ester, oxalanes and its mixture, it should be understood that at least 20vol% of the solvent includes ethylene carbonate；d）The porous carbon materials of positive electrode are selected from such material：The average-size in hole is more than 0.7nm and the material has greater than about 700m2The specific surface of/g；e）The non-porous carbon material of negative electrode is selected from and is inserted into ion and with no more than 150m2The material of the specific surface of/g；And f）After the number of assembling steps, with the maximum voltage up between 4 and 5 volts（Umax）Multiple trickle charge steps with the current density from 10mA/g to 400mA/g carry out the charging of ultracapacitor.Each charge step is separated by the self discharge under the electric current less than 5mA/g or the interstage of electric discharge with subsequent charge step.
Description
Technical field
Method the present invention relates to be used to assemble hybrid electrochemical system.
Background technology
It is well known that in the prior art, with reference to the storage of lithium rechargeable battery and electrochemical double layer capacitor (EDLC)
The hybrid super capacitor of principle has the energy density higher than standard EDLC, usually in 7Whkg-1Magnitude.Standard
Symmetrical cells unit (cell) of EDLC are made up of two identical capacitance electrodes.The electrical potential difference of such uncharged battery unit is 0V
And it is linearly increasing over time during the constant current (galvanostatic) of battery unit charges.During charging, positive electrode
Potential it is linearly increasing and potential of negative electrode linearly reduces.During discharging, cell voltage linearly reduces.In organic media
The symmetrical EDLC of the industry typically nominal voltages with 2.7V of middle operation, accordingly, during system charging and discharging, lithium battery
The electrode of type is characterized by the potential of practical stability.In order to increase the operating voltage of super capacitor, " lithium battery " class can be used
The electrode based on carbon of type substitutes the negative electrode of EDLC.
The subject matter to be solved in the hybrid super capacitor of this type be passivation layer formation and lithium to negative electrode
Insertion/insertion.In the first step, the passivation of negative electrode causes to be formed on this electrode during the first specific charging cycle
Intermediate layer.When there is layer, lithium ion is before insertion/insertion negative electrode by desolvation (desolvate).In the presence of good shape
Into passivation layer allow to be prevented during system circulation coming off for negative carbon electrode.Lithium be embedded into/insert in negative electrode until
Obtain Li~0.5C6Composition.Therefore, during the trickle charge/electric discharge of hybrid super capacitor, the potential of negative electrode keeps relative
Stabilization.
Under the current state of the art, different solution are usually selected to produce passivation layer and to negative electrode insertion/insertion
The lithium ion of q.s.
I) using lithium metal source to prevent electrolyte to be depleted, for example, being retouched in patent of invention EP-A1-1 400 996
State.
Ii ex situ insertion/insertion of the lithium to electrode active material) is carried out, for example, is ground by reactivity.
Iii) by the electrolyte solution comprising lithium ion, such as by the offer in JP2008-177263 is invented
The surface functional group of the positive carbon electrode of LiOH aqueous solution saturation activations.The lithium present in positive electrode can be then carried out to negative electricity
Insertion/insertion in extremely is without depleted of electrolyte.
Shortcoming using lithium metal is particularly expensive and industrialization is restricted.In addition, in current organic solvent, lithium
Metal can cause thermal runaway and therefore there is safety issue.
Ex situ for the compound of the insertion/insertion of lithium is produced equally with problem：It is for manufacturing energy stores
The purpose of system, subsequent material allows for being processed.In fact, known these materials easily occur with oxygen, water and nitrogen
Reaction.
Therefore, these three solutions are uneconomical and/or technically unsatisfactory.
From appearing in Journal of Power Sources, 177 (2008), the publication " High- of 643-651
energy density graphite/AC capacitor in organic electrolyte”(V.Khomenko,
E.Raymundo-Pinero and F.B é guin), it is also known that a kind of method for assembling hybrid super capacitor, i.e., it is a kind of
Electrochemical energy storage system includes, on the one hand, the negative electrode based on non-porous or only slight porous carbon (for example, graphite), institute
The electrode of the anode that electrode is normally used as in lithium battery is stated, and, on the other hand, it is typically used in electrochemical double layer capacitor
In positive electrode, i.e., based on nano-pore carbon, wherein using the lithium salts for existing in the electrolyte carry out insertion of the lithium at negative electrode/
Insertion.However, the battery unit for using is to provide the laboratory cells unit of fully big holder for conductive electrolyte, and
And be embedded in lithium/insert negative electrode during the composition of electrolyte keep constant.In the case of more compact system, the body of electrolyte
Product is restricted and lithium is embedded in/inserts negative electrode meeting depleted of electrolyte, and this causes the decline of systematic function.
The content of the invention
Inventor develops a kind of hybrid super capacitor, its shortcoming for allowing to overcome standing state technology.
Specifically, process according to the invention overcomes the shortcoming for providing solution in the prior art, i.e. by making
With, such as to be quoted in final publication, but the lithium salts of electrolyte carries out insertion/insertion of the lithium at negative electrode passes through
Lithium concentration in substantial increase electrolyte is exhausted with subsequent receiving.When ion is when exhausting influence electrical conductivity, selection electrolysis
The amount and concentration of matter exhaust the electrical conductivity and the power system for energy storage that keep electrolyte simultaneously to allow to receive this
Match somebody with somebody.The Li for existing in the electrolyte+A part for ion be used to form passivation layer at negative electrode and for being embedded in/inserting
Li~0.5C6Compound.
It is not contemplated by those skilled in the art before this invention, they did not always use this route, specifically
Ground, with conventional electrolysis matter (for example, with conventional ion compound LiPF6, the solvent of conventional electrolysis matter is at the standard conditions about
Saturation under 1.5mol/l, this concentration for the exhausting of solution is too low, so that the ion for existing in electrical conductivity and in the solution
Amount aspect be unacceptable) substantially obtain sufficiently high Li+Ion concentration is not apparent from.
Therefore, subject of the present invention is a kind of method for preparing hybrid super capacitor, and methods described is included at least
One assembling is based on the negative electrode of at least one material based on Karbate and based at least one material based on porous carbon
The stage of positive electrode, the electrode is separated by the chorista impregnated with liquid electrolyte from each other, the liquid electrolyte
At least one lithium salts in solution including at least one solvent；Then at least one first charging stages, the spy of methods described
Levy and be：
A) before first charging stage, the concentration of the ion lithium in the liquid electrolyte is more than or equal to
1.6mol/l,
B) lithium salts of the liquid electrolyte includes at least salt of 50 weight %, and the salt is selected from two (trifluoromethyls
Sulphonyl) imine lithium (LiTFSI) and its derivative, such as double (fluorine sulphonyl) imine lithiums (LiFSI) and double (pentafluoroethyl group sulphonyl) are sub-
Amine lithium (LiBETI)；
C) solvent of the liquid electrolyte includes at least such solvent of 80 volume %, and the solvent is selected from ring-type
Alkyl carbonate, specifically selected from ethylene carbonate (EC) and propylene carbonate (PC)；Acyclic alkyl carbonic ether, is specifically selected from
Dimethyl carbonate (DMC), diethyl carbonate (DEC) and carbonic acid isopropyl methyl ester (MiPC)；Lactone (such as β-and gamma lactone
And caprolactone)；Ester, such as ethyl acetate and ethyl butyrate (EB)；Oxalanes, such as glycol dimethyl ether (DME)；And its
Mixture, it should be understood that the solvent includes at least ethylene carbonate of 20 volume %；
D) material based on porous carbon of the positive electrode is selected from such material, wherein the average-size in the hole
There is greater than about 700m more than 0.7nm and the material2The specific surface of/g, especially, from 700 to 2000m2/ g (B.E.T. sides
Method).
E) material based on Karbate of the negative electrode is selected from such material, and the material can be embedded in/insert
The lithium ion and with less than or equal to 150m2/g, especially 80m2/g, specific surface；
F) after the assembling stage, with the maximum voltage (U up between 4 and 5 voltsmax) and from 10mA/g to
Several trickle charge stages under the current density of 400mA/g carry out the charging of ultracapacitor, and each charging stage passes through
The interstage of self discharge or electric discharge under the electric current less than 5mA/g separates with the subsequent charging stage.
In the embodiment of change, the trickle charge stage is further separated by the self discharge stage.
According to the present invention, self discharge or discharge regime under the trickle charge stage of stage f) and low current (are also known as
Relaxation stage) combination be referred to as forming circulation.The method according to the invention, forming circulation causes the formation of passivation layer and causes
Lithium-ion embeding/insertion negative electrode.The trickle charge stage causes the consumption of the lithium ion for existing in the electrolyte and causes it
Concentration declines.
The several successive stages to carry out the electric discharge under extremely low electric current or self discharge are selected so as to obtain total
Charging interval, this cause lithium spread/insert negative electrode.Under the particular case of graphite, the insertion of lithium causes Insertion compound
Li~0.5C6Formation.Therefore, when ultracapacitor is in operation, the potential of negative electrode keeps relative stability.
Brief description of the drawings
Fig. 1 shown during the energy stores process of ultracapacitor of the invention, be included in EC/DMC (1/1,
V/v) electrical conductivity (mS/cm) of the liquid electrolyte of the LiTFSI in mixture as the function of concentration (mol/l) variation diagram.
Fig. 2 shows：Ultracapacitor of the invention, after assembling, by chronoptentiometry
(chronopotentiometry) system is charged via the formation of the invention circulation including the charging stage, then 2
The relaxaton period of hour.
Fig. 3 shows the result of the circulation of ultracapacitor of the invention.
Fig. 4 show ultracapacitor of the invention as the time (second) two potentials of electrode (V) of function and
The change of voltage (V).
Fig. 5 shows the result of the circulation of ultracapacitor of the invention.
Fig. 6 shows two potentials of electrode (V) of function as the time (second) of the ultracapacitor according to comparative example
With the change of voltage (V).
Fig. 7 shows the result of the circulation of the ultracapacitor according to comparative example.
Fig. 8 show the function as the time (second) of the ultracapacitor according to comparative example formed circulation during
The voltage and potential change (V) of electrode.
Fig. 9 shows the result of the circulation of the ultracapacitor according to comparative example.
Figure 10 shows that ultracapacitor of the invention is forming the function as the time (second) during circulation
The change of voltage (V).
Figure 11 shows the result of the circulation of ultracapacitor of the invention.
Specific embodiment
Accompanying drawing 1 shown during the energy stores process of ultracapacitor of the invention, is included in EC/DMC (1/
1, v/v) electrical conductivity (mS/cm) of the liquid electrolyte of the LiTFSI in mixture as the function of concentration (mol/l) change
Figure.This figure shows the concentration of the lithium ion that high (point B) electrolyte is selected as compared to optium concentration (point A).Stage
F) charging/relaxation circulation allow to form passivation layer and allow lithium ion be embedded in/insert negative electrode.These circulations
The concentration of electrolyte is caused to drop to point A (optimal).Therefore can be obtained by the method according to the invention and correctly operate and have
There is unbroken performance while tolerating the ultracapacitor of the bright particularly greater than notable electrical potential difference of 4V.Therefore, in formation stages
It is last, the amount of lithium ion insertion negative electrode is sufficient so that during its operation, and the potential of system keeps relative constancy.According to this
The method of invention can be obtained has the super of bigger energy density than the electrochemical double layer ultracapacitor of prior art state
Capacitor.
According to a preferred embodiment of the invention, before the first charging stage, ion lithium in liquid electrolyte it is dense
Degree is more than or equal to about 2.0mol/l.
Also according to the preferred embodiments of the present invention, liquid electrolyte is selected from following lithium salts/solvent pair：
i)LiTFSI-EC/DMC(1/1；V/v) mixture；
ii)LiFSI-EC/DMC(1/1；V/v) mixture；
iii)LiBETI-EC/DMC(1/1；V/v) mixture；
iv)LiTFSI-EC/EB/DMC(1/1/3；V/v/v) mixture；
v)LiTFSI-EC/MiPC/DMC(2/1/3；V/v/v) mixture；
vi)LiTFSI-EC/DMC(1/2；V/v) mixture；
Usually, containing lithium ionic compound (separates to form Li in a solvent+The compound of ion) and select molten
The agent Walden that at the temperature that material is got together (specifically 20 DEG C to 25 DEG C) have maximum possible so as to electrolyte is accumulated.
Walden products Λ η are that viscosity (η units be mPa.s) is multiplied by the molar conductivity of compound (Λ=σ/C units are mS.cm-1
(mol.l-1)-1) product.Shown in following table 1 in known solvent mixture for the method according to the invention
Different liquids electrolyte based on LiTFSI Walden product, and be based only upon LiPF6Liquid electrolyte comparing：
Table 1
| Salt:LiTFSI | Electrical conductivity at 20 DEG C | Viscosity at 25 DEG C | Λη |
| EC/DMC | 9.3 | 3.52 | 32.7 |
| EC/EB/3DMC | 9.08 | 3.58 | 32.5 |
| 2EC/MiPC/3DMC | 9.83 | 3.46 | 34.0 |
| EC/2DME | 18.1 | 3.0 | 54.3 |
| EC/DEC | 6.8 | 3.25 | 22.1 |
| EC/PC/3DMC | 8 | 3.56 | 28.5 |
| Electrical conductivity at 20 DEG C | Viscosity at 25 DEG C | Λη | |
| EC/DMC | 11.20 | 3.50 | 39.2 |
| EC/PC/3DMC | 10.58 | 3.56 | 37.6 |
Note:In this table, the ratio of the solvent for using in the mixture is given by volume；For example, EC/DMC is meaned
Solvent to be made up of the mixture of isometric EC and DMC.
As shown in this table, selection to value have there is identical magnitude with general electrolyte, this confirms that they
Application advantage.
In addition to the above-mentioned lithium salts (mainly lithium salts) mentioned in point b) during statement of the invention, according to this hair
The liquid electrolyte that bright method can be used can additionally include LiPF6As additional lithium salts.
When liquid electrolyte includes LiPF6During as additional lithium salts, the latter is limited in point b) above with weighing less than
The amount of lithium salts be present in electrolyte, this amount represents most a quarters of the mole of the lithium salts referred in above-mentioned point b)
And relative to the lithium salts referred in above-mentioned point b) weight preferably from 1 weight of weight % to 10 %.This additional lithium salts
In the presence of being favourable, because the aluminum current collector of positive electrode can be passivated.
The material based on porous carbon of positive electrode is preferably chosen from carbide-derived carbon (CDC), porous CNT, porous
Carbon black, porous carbon fiber, carbon onion (carbon onion) or the carbon produced from coke (its porosity is increased by charging).
According to a preferred embodiment of the invention, the specific surface of the material based on porous carbon of positive electrode is changed to about from about 1200
1800m2/ g (B.E.T. methods).
The density of the material based on porous carbon of positive electrode preferably changes to 0.8g/cm from 0.53
Oxygen content in the material based on porous carbon of positive electrode is preferably smaller than 2 weight %.
It is preferred that positive electrode has from about 70 to about 120 μm of thickness.
The material based on Karbate of negative electrode is selected from the material that can be embedded in/insert lithium.Negative electrode based on Karbate
Material be preferably selected from graphite, cryogenic carbon (hard or soft), carbon black, non-porous CNT and non-porous carbon fiber.
The density of the material based on Karbate of negative electrode preferably changes to 1.9g/cm from 1.03.Negative electrode based on nothing
The specific surface (B.E.T. methods) of the material of hole carbon is preferably less than about 50m2/g。
It is preferred that negative electrode has from about 40 to about 70 μm of thickness.
According to a preferred embodiment of the invention, the ratio of the weight of the weight of positive electrode and negative electrode is more than or equal to 1.
This ratio ME+/ME-Preferably greater than or equal to 1 and less than or equal to 5.According to a highly advantageous elaboration of the invention, ratio ME+/ME-Deng
In 1.Preferably, this ratio is optimized to have identical charging number at negative electrodes.
Except the material (material based on porous carbon of positive electrode and the material based on Karbate of negative electrode) based on carbon
Outward, just and/or negative electrode usually also includes at least one cement and optionally assigns electronic conductivity (electron
Conductivity at least one medicament).
Cement can be selected from known in those skilled in the art and until the potential of the 5V relative to Li is
Electrochemically stable organic binder.In such cement, especially refer to：
The homopolymers and copolymer of-vinylidene for example, Kynoar (PVDF),
The copolymer of-ethene, propylene and diene,
The homopolymers and copolymer of-tetrafluoroethene,
The homopolymers and copolymer of-NVP,
The homopolymers and copolymer of-acrylonitrile,
The homopolymers and copolymer of-methacrylonitrile,
Etc..
When present, it is preferable that cement accounts for the weight % from about 5 weight % to about 15 relative to the gross weight of electrode.
The medicament for assigning electronic conductivity can be carbon, be preferably selected from carbon black (such as acetylene black), with high-ratio surface
Carbon black, such as Akzo Nobel are entitledThe sale product of EC-600JD, CNT, graphite or
The mixture of these materials.The medicament can also be the aqueous dispersion of carbon black or graphite, and for example Acheson is entitledThe sale product of EB-012.Other products can also be used.
According to the present invention, assign the material of electron conduction preferably with respect to the gross weight of electrode account for from about 1 weight % to
About 10 weight %.
According to the present invention, the composite for constituting electrode is preferably deposited on current collector, such as negative electrode
Copper current current-collector and the aluminium current collector for positive electrode.
Temperature for performing the method according to the invention can be environment temperature it is also possible to be higher than environment temperature (example
Such as, at 25 DEG C and 70 DEG C) between to increase the solubility of the lithium-containing compound in the solvent for using.According to alterative version,
The method according to the invention can be carried out at a temperature of more than or equal to 35 DEG C.Therefore, it can more than or equal to 35 DEG C
At a temperature of circulated to the charging/relaxation of the insertion/insertion of negative electrode for forming passivation layer and lithium.This can accelerate passivation
The formation of layer.
The liquid electrolyte that the method according to the invention can be used can additionally include one or more cosolvent, its
It is intended to increase ionic conductivity and extend temperature in use, such cosolvent is selected from alkyl fat, such as ethyl acetate, propionic acid first
Ester, ethyl propionate, ethyl butyrate, methyl butyrate etc. and its mixture.When they are used, cosolvent is preferably with respect to liquid
The gross weight of electrolyte accounts for the volume % from about 20 volume % to about 80.These cosolvent can improve the cold conditions of ultracapacitor
Energy.
According to a preferred embodiment of the invention, stage f) trickle charge stage each between relaxation stage
Duration is changed to about 3 hours from about 1.
According to a preferred embodiment of the invention, stage f) includes following sub：
1) sub 1, with the current density between 10 and 400mA/g be charged to up to more than or equal to 4.0V and less than etc.
In the voltage U of 5Vmax1, the relaxaton period of a length of 1 hour when then for minimum.
2) sub 2, are charged to the current density between 10 and 400mA/g and are up to more than Umax1And less than or equal to 5V
Voltage Umax2, the relaxaton period of a length of 1 hour when then for minimum.
3) sub 3, are charged to the current density between 10 and 400mA/g and are up to more than Umax2And less than or equal to 5V
Voltage Umax3, the relaxaton period of a length of 1 hour when then for minimum.
4) sub 4, are charged to the current density between 10 and 400mA/g and are up to more than Umax3And less than or equal to 5V
Voltage Umax4, the relaxaton period of a length of 1 hour when then for minimum.
5) sub 5, are charged to the current density between 10 and 400mA/g and are up to more than Umax4And less than or equal to 5V
Voltage Umax5, the relaxaton period of a length of 1 hour when then for minimum.
Form the sub 5 in circulation) can repeat, until in the case of 3- electrode batteries unit, being obtained at negative electrode
The stabilizing potential of about 0V is obtained, wherein can be with the potential of each electrode of monitoring system.In the case of 2- electrode batteries unit, according to
The result obtained in 3- electrode batteries unit or the electricity at the end of the relaxaton period from a sub to another sub
Suspend to form circulation during pressure identical (representing the stabilisation of the potential of negative electrode).
In the particular case of graphite, sub 5 can be repeated) until obtaining relative to Li+The stabilization of/Li about 0.1V is born
Electrode potential.The stage f) for carrying out method according to the present invention causes to form inlaid scheme Li at negative electrode~0.5C6。
The circulation of charging/relaxation can also include the stage more more or less than the stage described herein, it is also possible to which change is filled
Piezoelectric voltage.
The present invention is shown by subsequent example, however, it does not lie in limitation.
Note, the product obtained from the method according to the invention be included in point d) and e) described in electrode and be included in a little
The electrolyte of lithium salts and solvent described in b) and c).On the other hand, the concentration of the lithium in the electrolyte of final products can be with
Less than the threshold value for limiting in the disclosure.
It should also be noted that the negative electrode of final products be graphite electrode and formed inlaid scheme preferably from about have rank
Section 2 is embedded in, i.e. Li~0.5C6。
Example 1
According to the present invention, hybrid super capacitor is prepared for according to subsequent method：
- positive electrode：The porous activation carbon (specific surface (S of 80 weight %BET)=1670m2/ g), the PVDF of 10 weight % and
The carbon black of 10 weight %.This composite electrode material is applied on the aluminium current collector with 30 μm of thickness.Coating
Thickness (after drying and suppressing)：100μm.
- negative electrode：The graphite of the entitled SLP30 of the Timcal sale of 91 weight %, the PVDF and 1 weight of 8 weight %
Measure the carbon black of %.This composite electrode material is applied on copper collector.The thickness of coating：50μm.
- the electrolyte for using：1:2mol/l LiTFSI in 1 (v/v) EC/DMC mixtures.
- Li+/Li reference electrodes are added to monitor the potential change of negative electrodes.Note, in assembly including this electricity
Pole is only used for measuring purpose and does not form intact part of the invention.
After assembling, by chronoptentiometry (chronopotentiometry), via including the charging stage according to this
The formation circulation of invention is charged to system, the then relaxaton period of 2 hours, as described in fig 2, the wherein voltage of electrode
With the function that potential (volt) is time (second).Concern is charged (in 37.2mA/g)/the circulation of self discharge.At the end of circulation
The voltage of system is 4.2V.
Select negative electrode feature so as to chargings/self discharge circulate terminate after its relative to Li+The potential of/Li is about
0.1V, the stage 2 being approximately corresponding in lithium to graphite is embedded in.
Then, at ambient temperature, in Umax=4.2V and UminThe perseverance electricity of ± 0.65A/g is carried out between=1.5V to system
Stream circulation.Charging and discharging of the constant current circulation corresponding to system.
The result of this circulation, wherein gravimetric (F.g are shown in accompanying drawing 3-1) it is expressed as the function of cycle-index.Accompanying drawing
4 show during first circulation and after 500 times circulate as two potentials of electrode (V) of function of time (second) and electricity
Press the change of (V).
Also measure the self discharge of two electrode systems after 500 circulations.Then, voltage is kept for 30 minutes simultaneously in 4.2V
And then record self discharge (accompanying drawing 5, wherein voltage (V) are the functions of time (hour)).
The performance formed after circulating of system is illustrated in following table 2.
Comparative example 1
It is prepared for not according to symmetrical ultracapacitor of the invention according to subsequent method.
- positive electrode：The porous activation carbon (specific surface (S of 80 weight %BET)=1670m2/ g), the PVDF of 10 weight % and
The carbon black of 10 weight %.This composite electrode material is applied on the aluminium current collector with about 30 μm of thickness.Coating
Thickness：100μm.
- negative electrode：It is identical with positive electrode, the porous activation carbon (specific surface (S of 80 weight %BET)=1670m2/ g), 10 weights
Measure the carbon black of the PVDF and 10 weight % of %.This composite electrode material is applied to the aluminium electric current current collection with about 30 μ m thicks
On device.The thickness of coating：100μm.
Notice that two electrodes are identical with the positive electrode of example 1 here.
- the electrolyte for using：1:2mol/l LiTFSI in 1 (v/v) EC/DMC mixtures.
- addition Li+/ Li reference electrodes are to monitor the potential change of negative electrodes.
After assembling, at ambient temperature, in Umax=4.2V and UminThe perseverance of ± 0.65A/g is carried out between=1.5V to system
Current cycle.Because the high de-agglomeration of the electrolyte at positive electrode, it is impossible to carry out constant current circulation (0.65A/g).Relative to
Li+The potential of the positive electrode of/Li is higher than 5V, and as shown in Figure 6, the voltage and potential (volt) of wherein electrode are time (seconds)
Function.
The performance of system is shown in table 2 below.
Comparative example 2
It is prepared for not according to symmetrical ultracapacitor of the invention, according in comparative example 1 according to subsequent method
Description.
- positive electrode：The porous activation carbon (specific surface (S of 80 weight %BET)=1670m2/ g), the PVDF of 10 weight % and
The carbon black of 10 weight %.This composite electrode material is applied on the aluminium current collector with about 30 μ m thicks.Coating
Thickness：100μm.
- negative electrode：It is identical with positive electrode, the porous activation carbon (specific surface (S of 80 weight %BET)=1670m2/ g), 10 weights
Measure the carbon black of the PVDF and 10 weight % of %.This composite electrode material is applied to the aluminium electric current current collection with about 30 μ m thicks
On device.The thickness of coating：100μm.
- the electrolyte for using：1:2mol/l LiTFSI in 1 (v/v) EC/DMC mixtures.
Addition Li+/ Li reference electrodes are to monitor the potential change of negative electrodes.
After assembling, at ambient temperature, in Umax=2.5V and UminThe perseverance electricity of ± 0.65A/g is carried out between=0V to system
Stream circulation.The result of this circulation, wherein gravimetric (F.g are shown in accompanying drawing 7-1) function that is expressed as cycle-index (most goes up
The curve in face).
The performance of system is shown in table 2 below.
Comparative example 3
In this example, be prepared for not according to the present invention and with the symmetrical ultracapacitor of identical of comparative example 2, but
It is wherein to be used in 1:(the LiPF of LiTFSI+1mol% of the 1.6mol/l in 1 (v/v) EC/DMC mixtures6) substitute electrolyte.
Equally, limiting voltage is to 2.5V.The circulation of ± 0.65A/g constant currents is carried out to system at ambient temperature.Figure 7 illustrates finishing
Really (intermediate curve).
The performance of system is shown in table 2 below.
Comparative example 4
In this example, be prepared for not according to the present invention and with the symmetrical ultracapacitor of identical of comparative example 2, but
It is wherein to be used in 1:(the LiPF of LiTFSI+1mol% of the 2mol/l in 1EC/DMC mixtures6) substitute electrolyte.Voltage is same
Sample is limited to 2.5V, carries out the circulation of ± 0.65A/g constant currents to system at ambient temperature.Figure 7 illustrates result (under most
The curve in face).
The performance of system is shown in table 2 below.
Comparative example 5
In this example, be prepared for not according to the present invention and with the symmetrical ultracapacitor of identical of comparative example 2, but
It is the TEABF with the 1mol/l in acetonitrile in area4Substitute electrolyte.
After assembling, system is electrically charged same stop voltage to 2.5 volts.± 0.65A/ is carried out to system at ambient temperature
G constant currents are circulated.
The performance of system is shown in table 2 below.
Comparative example 6
It is prepared for not according to hybrid super capacitor of the invention according to subsequent method.
- positive electrode：The porous activation carbon (specific surface (S of 80 weight %BET)=1670m2/ g), the PVDF of 10 weight % and
The carbon black of 10 weight %.This composite electrode material is applied on the aluminium current collector with about 30 μ m thicks.Coating
Thickness：100μm.
- negative electrode：The graphite of the entitled SLP30 that the Timcal of 91 weight % sells, the PVDF and 1 weight of 8 weight %
Measure the carbon black of %.This composite electrode material is applied on copper collector.The thickness of coating：50μm.
Note, negative electrodes are identical with example 1.
- the electrolyte for using：1:2mol/l LiTFSI+1%LiPF in 1 (v/v) EC/DMC mixtures6。
- addition Li+/ Li reference electrodes are to monitor the potential change of negative electrodes.
After assembling, by the DC charging for being up to 4.4V be constructed without it is of the invention form circulation, then 2 hours from
Discharge cycle.The function as the time (second) shown in Figure 8 in the voltage and potential for forming the electrode during circulation
Change (V).
At ambient temperature, in Umax=4.4V and UminThe circulation of ± 0.65A/g constant currents is carried out between=1.5V to system.
The result of constant current circulation, wherein gravimetric (F.g are shown in accompanying drawing 9-1) it is expressed as the function of cycle-index.
The performance formed after circulating of system is illustrated in following table 2.
Embodiment according to the present invention 2
Hybrid super capacitor of the invention is prepared for according to subsequent method.
- positive electrode：The porous activation carbon (specific surface (SBET)=1670m of 80 weight %2/ g), the PVDF of 10 weight % and
The carbon black of 10 weight %.This composite electrode material is applied on the aluminium current collector with about 30 μ m thicks.Coating
Thickness：100μm.
- negative electrode：The graphite of the title SLP30 of the Timcal sale of 91 weight %, the PVDF of 8 weight % and 1 weight %
Carbon black.This composite electrode material is applied on copper collector.The thickness of coating：50μm.
Note, negative electrodes are identical with example 1 and do not occur lithium gold by contrast, in systems with example 1
Belong to the reference electrode for constituting.
- the electrolyte for using：1:2mol/l LiTFSI+1mol%LiPF in 1 (v/v) EC/DMC mixtures6。
After assembling, by chronoptentiometry, system is filled via the formation of the invention circulation including the charging stage
Electricity, the then relaxaton period of 2 hours, as described in fig 2, wherein voltage (volt) is the function of time (second).Concern
Charge (in 37.2mA/g)/self discharge circulation.The maximum voltage of system is 4.4V.
The change in the voltage (V) for forming the function as the time (second) during circulation shown in Figure 10.
At ambient temperature, in Umax=4.4V and UminThe circulation of ± 0.65A/g constant currents is carried out between=1.5V to system.
The result of this circulation, wherein gravimetric (F.g are shown in accompanying drawing 11-1) it is expressed as the function of cycle-index.
The performance formed after circulating of system is illustrated in following table 2.
The performance of the different system for preparing in the above-described example is listed in the table below in 2：
Table 2
The combination of these results shows that first, ultracapacitor of the invention can be obtained than other capacitors more
Gravimetric (being compared with comparative example 1 and 5 by example 1 and 2) high.In addition, they can be operated with voltage higher
(4.2V).The two factors cause that the energy density of these ultracapacitors is dramatically increased (5 to 10 times).The latter is caused for phase
Same size, can transmit bigger power simultaneously therefore particularly advantageous.
In addition, these hybrid super capacitor life-spans are good because at least 500 times circulations, they gravimetric (and
And therefore their energy density) relative constancy is kept, and the situation of the symmetrical ultracapacitor of same electrolyte is different.
Initial capacity in example 2 than example 1 in it is higher because maximum voltage is equally higher.On the other hand, note
Meaning, during circulating, probably due to the decline of capacity is bigger in the case of the erosion of aluminium, example 2, although slightly adding LiPF6
To electrolyte, situation remains unchanged.
Additionally, it is noted that the formation circulation described in stage f) is it possible to assure that ultracapacitor is stablized in time
(unlike other charging processes, as noticed according to comparative example 6) and can obtain with high-energy-density and same reliability
Ultracapacitor.
Furthermore it is possible to the selection of the more preferably electrolyte of operation hybrid super capacitor is not for those skilled in the art
Obvious selection.Because, it can be clearly seen that these electrolyte pair are not optimal with symmetrical ultracapacitor.
The gravimetric and energy density of comparative example 2 to 4 are less than the 1mol/l TEABF in typical acetonitrile4Conventional electrolysis matter
Obtained in (comparative example 5).
Therefore, the invention enables that can obtain hybrid super capacitor, this causes symmetrical compared to prior art state
Ultracapacitor, increases operating voltage and therefore transmission higher energy density.
Claims (25)
1. a kind of method for preparing hybrid super capacitor, methods described includes at least one assembling based at least one base
In the negative electrode of the material of Karbate and the positive electrode based at least one material based on porous carbon stage, the electrode lead to
Cross disconnected from each other with the chorista of liquid electrolyte dipping, the liquid electrolyte includes at least one at least one solvent
The solution of lithium salts；Then at least one first charging stage, methods described is characterised by：
A) before first charging stage, the concentration of the lithium ion in the liquid electrolyte is more than or equal to
1.6mol/L,
B) lithium salts of the liquid electrolyte include at least 50 weight % selected from two (trimethyl fluoride sulfonyl) imine lithiums
(LiTFSI) and its derivative lithium salts；
C) solvent of the liquid electrolyte includes at least such solvent of 80 volume %, and the solvent is selected from cyclic alkyl
Carbonic ester；Acyclic alkyl carbonic ether；Lactone；Ethyl acetate and ethyl butyrate；Glycol dimethyl ether (DME) and its mixture, institute
Stating solvent includes at least ethylene carbonate of 20 volume %；
D) material based on porous carbon of the positive electrode is selected from such material, wherein the average-size in the hole is more than
0.7nm and the material have by B.E.T. methods obtain more than 700m2The specific surface of/g；
E) material based on Karbate of the negative electrode is selected from such material, and the material is inserted into the lithium ion
And with less than or equal to 150m2The specific surface of/g；
F) after the assembling stage, with the maximum voltage U up between 4 and 5 voltsmaxWith from 10mA/g to 400mA/g
Current density under several trickle charge stages carry out the charging of the ultracapacitor, each charging stage is by small
Separated with the subsequent charging stage in the self discharge under the current density of 5mA/g or the interstage of electric discharge.
2. method according to claim 1, it is characterised in that before first charging stage, in the liquid electrolyte
Lithium ion concentration be more than or equal to 2.0mol/L.
3. method according to claim 1, it is characterised in that the liquid electrolyte is selected from following lithium salts/solvent pair：
I) the LiTFSI-EC/DMC mixtures of 1/1 volume ratio；
Ii) the LiFSI-EC/DMC mixtures of 1/1 volume ratio；
Iii) the LiBETI-EC/DMC mixtures of 1/1 volume ratio；
Iv) the LiTFSI-EC/EB/DMC mixtures of 1/1/3 volume ratio；
V) the LiTFSI-EC/MiPC/DMC mixtures of 2/1/3 volume ratio；
Vi) the LiTFSI-EC/DMC mixtures of 1/2 volume ratio.
4. the method for any one in claim 1-3, it is characterised in that the liquid electrolyte additionally includes LiPF6
As additional lithium salts.
5. method according to claim 4, it is characterised in that the LiPF6To be the lithium salts of the liquid electrolyte to the maximum
The mole of a quarter of mole be present in the liquid electrolyte.
6. the method for any one in claim 1-3, it is characterised in that the positive electrode it is described based on porous carbon
Material is selected from carbide-derived carbon (CDC), porous CNT, porous carbon black, porous carbon fiber, carbon onion and is produced by coke
Raw carbon.
7. the method for any one in claim 1-3, it is characterised in that the positive electrode it is described based on porous carbon
The specific surface obtained by B.E.T. methods of material changes to 1800m from 12002/g。
8. the method for any one in claim 1-3, it is characterised in that the positive electrode it is described based on porous carbon
The density of material changes to 0.8g/m from 0.53。
9. the method for any one in claim 1-3, it is characterised in that the positive electrode it is described based on porous carbon
The oxygen content of material is less than 2 weight %.
10. the method for any one in claim 1-3, it is characterised in that the positive electrode has from 70 to 120 μm
Thickness.
The method of 11. any one in claim 1-3, it is characterised in that the negative electrode it is described based on Karbate
Material be selected from graphite, cryogenic carbon, carbon black, non-porous CNT and non-porous carbon fiber.
The method of 12. any one in claim 1-3, it is characterised in that the negative electrode it is described based on Karbate
The density of material change to 1.9g/m from 1.03。
The method of 13. any one in claim 1-3, it is characterised in that the negative electrode it is described based on Karbate
Material the specific surface be less than 50m2/g。
The method of 14. any one in claim 1-3, it is characterised in that the negative electrode has from 40 to 70 μm
Thickness.
The method of 15. any one in claim 1-3, it is characterised in that the weight of the positive electrode is to the negative electricity
The ratio of the weight of pole is more than or equal to 1.
16. methods according to claim 15, it is characterised in that the weight of the positive electrode is to described in the negative electrode
The ratio of weight is more than or equal to 1 and less than or equal to 5.
The method of 17. any one in claim 1-3, it is characterised in that the positive electrode and/or the negative electrode
The material additionally includes at least one cement.
18. according to the method for any one in claim 17, it is characterised in that the positive electrode and/or the negative electrode
The material additionally includes assigning at least one conductive agent of electronic conductivity.
The method of 19. any one in claim 1-3, it is characterised in that methods described is in environment temperature or 25
DEG C and 70 DEG C at a temperature of between carry out.
The method of 20. any one in claim 1-3, it is characterised in that in the trickle charge stage of stage f)
Each between the duration in the interstage changed to 3 hours from 1.
The method of 21. any one in claim 1-3, it is characterised in that the scala media described in stage f)
Section is self discharge.
The method of 22. any one in claim 1-3, it is characterised in that stage f) includes following sub：
1) sub 1, is charged to up to more than or equal to 4.0V and less than or equal to 5V with the current density between 10 and 400mA/g
Voltage Umax1, the relaxaton period of a length of 1 hour when then for minimum；
2) sub 2, are charged to the current density between 10 and 400mA/g and are up to more than Umax1And the electricity less than or equal to 5V
Pressure Umax2, the relaxaton period of a length of 1 hour when then for minimum；
3) sub 3, are charged to the current density between 10 and 400mA/g and are up to more than Umax2And the electricity less than or equal to 5V
Pressure Umax3, the relaxaton period of a length of 1 hour when then for minimum；
4) sub 4, are charged to the current density between 10 and 400mA/g and are up to more than Umax3And the electricity less than or equal to 5V
Pressure Umax4, the relaxaton period of a length of 1 hour when then for minimum；
5) sub 5, are charged to the current density between 10 and 400mA/g and are up to more than Umax4And the electricity less than or equal to 5V
Pressure Umax5, the relaxaton period of a length of 1 hour when then for minimum.
23. methods according to claim 1, it is characterised in that the derivative of two (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI)
Selected from double (fluorine sulphonyl) imine lithiums (LiFSI) and double (pentafluoroethyl group sulphonyl) imine lithiums (LiBETI).
24. methods according to claim 1, it is characterised in that preparing cyclic alkyl carbonate is selected from ethylene carbonate (EC) and carbonic acid
Sub- propyl ester (PC).
25. methods according to claim 1, it is characterised in that acyclic alkyl carbonic ether is selected from dimethyl carbonate (DMC), carbonic acid
Diethylester (DEC) and carbonic acid isopropyl methyl ester (MiPC).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1155048 | 2011-06-09 | ||
| FR1155048 | 2011-06-09 | ||
| PCT/FR2012/050837 WO2012172211A1 (en) | 2011-06-09 | 2012-04-17 | Method for assembling a hybrid lithium supercapacitor |
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| CN103733290B true CN103733290B (en) | 2017-06-30 |
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| US (1) | US9136066B2 (en) |
| EP (1) | EP2718944B1 (en) |
| JP (1) | JP6067003B2 (en) |
| KR (1) | KR101985789B1 (en) |
| CN (1) | CN103733290B (en) |
| AU (1) | AU2012270250B2 (en) |
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| JP2014225574A (en) * | 2013-05-16 | 2014-12-04 | 住友電気工業株式会社 | Capacitor and charge and discharge method thereof |
| US10756390B2 (en) * | 2014-11-20 | 2020-08-25 | Ses Holdings Pte. Ltd. | Concentrated electrolyte solution |
| JP2017139435A (en) * | 2016-01-29 | 2017-08-10 | 日本ケミコン株式会社 | Electrode, capacitor using the same, and electrode manufacturing method |
| WO2017131016A1 (en) * | 2016-01-29 | 2017-08-03 | 日本ケミコン株式会社 | Electrode, capacitor in which electrode is used, and method for manufacturing electrode |
| CN109314277B (en) * | 2016-06-08 | 2020-07-31 | 远景Aesc 日本有限公司 | Nonaqueous electrolyte secondary battery |
| US10600583B1 (en) | 2018-08-30 | 2020-03-24 | King Saud University | Method of making a porous nitrogen-doped carbon electrode from biomass |
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| CN101335364A (en) * | 2007-06-28 | 2008-12-31 | 比亚迪股份有限公司 | Li-ion secondary battery formation method |
| CN101385183A (en) * | 2006-04-28 | 2009-03-11 | 松下电器产业株式会社 | Electrochemical energy storage device |
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| JP4618929B2 (en) * | 2000-05-09 | 2011-01-26 | 三菱化学株式会社 | Activated carbon for electric double layer capacitors |
| CA2327370A1 (en) * | 2000-12-05 | 2002-06-05 | Hydro-Quebec | New method of manufacturing pure li4ti5o12 from the ternary compound tix-liy-carbon: effect of carbon on the synthesis and conductivity of the electrode |
| AU2002244957B2 (en) | 2001-06-29 | 2005-07-21 | Subaru Corporation | Organic electrolyte capacitor |
| KR100534845B1 (en) * | 2003-12-30 | 2005-12-08 | 현대자동차주식회사 | Method for Manufacturing Nano-structured Electrode of Metal Oxide |
| JP2006024785A (en) * | 2004-07-08 | 2006-01-26 | Tomiyama Pure Chemical Industries Ltd | Electric double layer capacitor and nonaqueous electrolytic solution therefor |
| US20090023074A1 (en) * | 2005-04-19 | 2009-01-22 | Tooru Matsui | Nonaqueous electrolyte solution, and electrochemical energy-storing device and nonaqueous-electrolyte- solution secondary battery using the same |
| RU2391732C2 (en) * | 2005-06-24 | 2010-06-10 | ЮНИВЕРСАЛ СУПЕРКАПАСИТОРЗ ЭлЭлСи | Heterogeneous electrochemical supercapacitor and method of manufacturing |
| JP2008177263A (en) | 2007-01-17 | 2008-07-31 | Sanyo Electric Co Ltd | Active carbon electrode and its manufacturing method, electric double-layer capacitor, and hybrid capacitor |
| JP4918418B2 (en) * | 2007-06-13 | 2012-04-18 | アドバンスト・キャパシタ・テクノロジーズ株式会社 | Lithium ion pre-doping method and method for producing lithium ion capacitor storage element |
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| JP2010205846A (en) * | 2009-03-02 | 2010-09-16 | Asahi Kasei Corp | Nonaqueous lithium type electricity storage element |
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| CN1400614A (en) * | 2001-07-25 | 2003-03-05 | 旭硝子株式会社 | Secondary power supply |
| CN101385183A (en) * | 2006-04-28 | 2009-03-11 | 松下电器产业株式会社 | Electrochemical energy storage device |
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Also Published As
| Publication number | Publication date |
|---|---|
| AU2012270250B2 (en) | 2016-07-21 |
| US9136066B2 (en) | 2015-09-15 |
| JP6067003B2 (en) | 2017-01-25 |
| RU2591846C2 (en) | 2016-07-20 |
| EP2718944A1 (en) | 2014-04-16 |
| UA110650C2 (en) | 2016-01-25 |
| BR112013031315A2 (en) | 2016-11-29 |
| CN103733290A (en) | 2014-04-16 |
| US20140325807A1 (en) | 2014-11-06 |
| KR20140073479A (en) | 2014-06-16 |
| CA2835124A1 (en) | 2012-12-20 |
| EP2718944B1 (en) | 2017-08-02 |
| WO2012172211A1 (en) | 2012-12-20 |
| ES2641533T3 (en) | 2017-11-10 |
| IL229655A0 (en) | 2014-01-30 |
| CA2835124C (en) | 2019-06-25 |
| IL229655A (en) | 2017-06-29 |
| RU2013158932A (en) | 2015-07-20 |
| JP2014520395A (en) | 2014-08-21 |
| AU2012270250A1 (en) | 2013-12-12 |
| KR101985789B1 (en) | 2019-06-04 |
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